Mössbauer Spectroscopic Studies of Chlorostannate(II) Complexes in Frozen Aqueous Solutions

Mössbauer parameters of frozen aqueous solutions of Sn(ClO₄)₂ in 0.5 M HClO₄ did not change with the concentration of NaClO₄, so that it was used to keep the ionic strength at the desired level. When NaCl was added into Sn(ClO₄)₂ solutions, isomer shift did not change, but quadrupole splitting did. Therefore, stability constants were calculated from the quadrupole splitting data, which were in good agreement with the published values. The observed spectra could be resolved into components.     

Mössbauer Spectroscopic Studies of Supported α-Fe2O3 and Fe Catalysts II: The Effect of the Second Metal Addition

The effect of the addition of a second metals such as Zn and Ni on the calcinaton and reduction of alumina, magnesia and silicasupported iron catalysis with total iron loading of 5wt% is investigated by Mössbauer spectroscopy. It is shown that the reducibility of supported α-Fe₂O₃ is gradually increased by adding the second metal. The values of the magnetic hyperfine field obtained from Mössbauer spectra for the Zn or Ni-added α-Fe₂O₃ or Fe catalysts decreased with increasing second metal loading.     

固相萃取–高效液相色谱法测定豆芽中4-氯苯氧乙酸钠和6-苄基腺嘌呤的残留量

建立了测定豆芽中4-氯苯氧乙酸钠和6-苄基腺嘌呤的固相萃取–高效液相色谱法。样品以0.1 mol/L的盐酸溶液为提取剂,经C18固相萃取柱净化处理,以乙腈–10 mmol/L乙酸铵水溶液(体积比25∶75)为流动相,Tech Mate C_(18)–ST色谱柱分离,4-氯苯氧乙酸钠和6-苄基腺嘌呤的紫外检测波长分别为228 nm和267 nm,色谱峰面积外标法定量。在0.50~100.00 mg/L浓度范围内,4-氯苯氧乙酸钠的相关系数为0.999 8,精密度在1.3%~8.2%之间(n=6),回收率在103.1%~109.0%之间;在0.05~10 mg/L浓度范围内,6-苄基腺嘌呤相关系数为0.999 9,精密度在0.9%~3.8%之间(n=6),回收率在88.0%~95.4%之间。4-氯苯氧乙酸钠和6-苄基腺嘌呤的检出限(S/N=3)分别为0.24,0.02 mg/kg。该法可以同时完成豆芽中4-氯苯氧乙酸钠和6-苄基腺嘌呤的分析检测。     

Slc11a2第六跨膜区在十二烷基磷酰胆碱胶束中的结构

采用圆二色谱和核磁共振波谱研究了Slc11a2第六跨膜区在十二烷基磷酰胆碱(DPC)膜模拟环境中的结构和定位.结果表明,Slc11a2第六跨膜区在DPC胶束中N端和C端各形成一小段α螺旋,两段螺旋中间通过高度灵活的区域连接,整个肽插入到DPC胶束中.H267A突变使螺旋长度变长,H272A突变使螺旋长度略有变短,突变后结构的变化可能和蛋白功能缺失相关.     

聚6-羟基己酸碱性条件下的水解反应研究

探究了碱性条件下聚6-羟基己酸水解反应的机理和最优化工艺条件。实验过程中选用碱度较大的氢氧化钠及碱度较小的碳酸氢钠作为反应试剂。研究表明:碱度不同,其反应机理,反应工艺条件亦不同。碱度越大,OH~-浓度越大,亲核基团[OH~-]直接进攻聚6-羟基己酸的酯基结构,使酯基键发生断裂反应,生成小分子的6-羟基己酸;反应工艺条件缓和,在100℃的集热式恒温加热磁力搅拌器中既可完全解聚。碱度大的氢氧化钠参与反应的最优化工艺条件:氢氧化钠/聚6-羟基己酸摩尔比为4.4,乙二醇/聚6-羟基己酸摩尔比为6.5,水用量100g,催化剂0.1g,反应时间2h,反应温度100℃条件下,6-羟基己酸产率达到84.07%;碱度小的碳酸氢钠钠参与反应的最优化工艺条件:碱度越小,OH~-浓度越小,在反应初期亲核基团[-OCH_2CH_2OH]占主导地位,发生醇解反应的概率大,整个反应体系为醇解反应与水解反应相互促进进行;反应工艺条件苛刻,须在180℃密闭高压釜中完全解聚。碳酸氢钠/聚6-羟基己酸摩尔比为1.1,乙二醇/聚6-羟基己酸摩尔比为3,水用量100g,催化剂0.1g,反应时间1h,反应温度180℃~190℃条件下,6-羟基己酸产率达到90.38%。在整个反应系统中,乙二醇作为溶剂来使用。     

Oxoaminium salts as initiators for cationic polymerization of vinyl monomers

Oxoaminium salt ( 1 ), derived from 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 2 ) by one-electron oxidation, could be an initiator for cationic polymerization of vinyl monomers such as isobutyl vinyl ether (IBVE), 2,3-dihydrofuran, p-methoxystyrene, N-vinyl pyrrolidone, etc., to give the corresponding polymers, when 1 had a low nucleophilic counter anion. Formation of the adducts of 1 and IBVE as well as ¹H-NMR and IR data suggested the formation of polymers containing N? O? C structure as the polymer head group. In the polymerization of IBVE, the effects of solvent and concentration of 1 were little observed, however the polymerization rate was dependent on temperature. Furthermore, the thermal reaction of the polymers obtained, which were regarded as prepolymers for block copolymerization and polymeric initiators for radical polymerization, was studied. For example, poly(2-benzylidene-1,3-dioxane) obtained by the polymerization of 2-benzylidene-1,3-dioxane with oxoaminium hexafluoroantimonate ( 1, X = SbF₆) was employed as an initiator for radical polymerization of MMA to give its block copolymer with PMMA. © 1993 John Wiley & Sons, Inc.     

Radical alternating copolymerization of vinyl ethers

New alternating equimolar copolymers of electrophilic trisubstituted ethylenes, methyl 3-phenyl-2-cyanopropenoate and 2-phenyl-1,1-dicyanoethene, with ethyl, n-butyl, i-butyl, t-butyl, 2-chloroethyl, and phenyl vinyl ethers were prepared by free radical initiation. Chemical compositions of the copolymers are 1 : 1 in broad ranges of monomer ratios. The copolymerization rate of both electrophilic monomers with the vinyl ethers increase in the series 2-chloroethyl > ethyl > phenyl > n-butyl > i-butyl > t-butyl. These variations in the reactivity of the vinyl ethers are discussed in terms of their preferred conformations in donor-acceptor complexes with electrophilic trisubstituted ethylenes. © 1993 John Wiley & Sons, Inc.     

Synthesis and Structure of the Centered Cluster Compound Ba3(Zr6Cl18Be)

Reaction of powdered Zr with ZrCl₄, BaCl₂ and Be in suitable proportions in a Ta container at 800°C produces the title compound. Suitable monocrystals for X-ray diffraction were obtained from reactions to which a comparable amount of Hg₂Cl₂ had been added. The structure of Ba₃Zr₆Cl₁₈Be is a superstructure of the K₂ZrCl₆ · Zr₆Cl₁₈H type (R3 c, Z = 6; a = 9.6852 (9) Å, c = 52.52 (1) Å; R, R_w = 2.7, 3.2% for 826 independent reflections, 2θ ≤ 50°). Trigonally compressed [Zr₆(Be)Cl₁₂ⁱ]Cl₆^a clusters are interconnected by six-coordinate barium atoms that lie in Cl^a antiprisms (a twisted version of the Zr^IV site) while (9 + 3)-coordinate barium substitutes for potassium within chlorine layers. Distortions associated with the size and field of barium are responsible for the superstructure and for differences from other analogues.